A cross-metathesis approach for polymetallic [FeFe]-hydrogenase mimics.

A method has been developed for synthesizing [FeFe]-H2ase mimics with diverse structures and properties, employing cross-metathesis of olefins. Vinylmetallocenes (5 and 6) and vinyl half-sandwich complexes (10 and 11) have been used as cross-metathesis partners with [FeFe]-H2ase mimics (4, 8, and 9) bearing a double bond in the moiety attached to the ADT-bridge nitrogen. Electrochemical studies of these complexes, encompassing metallocene-type (7a-b, 12a-b, and 13a-b) as well as half-sandwich derivatives (12c and 13c-d), have demonstrated that the introduction of a redox unit has a marginal impact on the reduction potential of these [FeFe]-H2ase mimics. The application of this cross-metathesis approach has allowed the synthesis of [FeFe]-H2ase mimics featuring an Ir(III) electrochemical antenna (16-18) as well as systems having an electron-donor-photosensitizer structure (ED-PS) (23). The electrocatalytic properties of these complexes have been elucidated through electrochemical studies.

Design of a Multi-Point Kinematic Coupling for a High Precision Telescopic Simultaneous Measurement System.

This paper covers the design of a new multi-point kinematic coupling specially developed for a high precision multi-telescopic arm measurement system for the volumetric verification of machine tools with linear and/or rotary axes. The multipoint kinematic coupling allows the simultaneous operation of the three telescopic arms that are registered at the same time to a sphere fixed on the machine tool spindle nose. Every coupling provides an accurate multi-point contact to the sphere, avoiding collisions and interferences with the other two multi-point kinematic couplings, and generating repulsion forces among them to ensure the coupling's fingers interlacing along the machine tool x/y/z travels in the verification process. Simulation presents minimal deformation of the kinematic coupling under load, assuring the precision of the sphere-to-sphere distance measurement. Experimental results are provided to show that the multi-point kinematic coupling developed has repeatability values below ±1.2 µm in the application.

Configuration Optimisation of Laser Tracker Location on Verification Process.

Machine tools are verified and compensated periodically to improve accuracy. The main aim of machine tool verification is to reduce the influence of quasi-static errors, especially geometric errors. As these errors show systematic behavior, their influence can be compensated. However, verification itself is influenced by random uncertainty sources that are usually not considered but affect the results. Within these uncertainty sources, laser tracker measurement noise is a random error that should not be ignored and can be reduced through adequate location of the equipment. This paper presents an algorithm able to analyse the influence of laser tracker location based on nonlinear optimisation, taking into consideration its specifications and machine tool characteristics. The developed algorithm uses the Monte Carlo method to provide a zone around the machine tool where the measurement system should be located in order to improve verification results. To achieve this aim, different parameters were defined, such as the number of tests carried out, and the number and distribution of points, and their influence on the error due to the laser tracker location analysed.

Revisiting the photochemical synthesis of [FeFe]-hydrogenase mimics: reaction optimization, mechanistic study and electrochemical behaviour.

The photoreaction of [(µ-S)2Fe2(CO)6] and alkenes or alkynes has been optimized to readily obtain functionalized [FeFe]-hydrogenase mimics. Irradiation under low CO pressure in THF produces the corresponding photo-adducts in good/acceptable (alkenes/alkynes) yields, with retention of the starting olefin stereochemistry. DFT-calculations provide plausible reaction pathways in both, singlet and triplet states. The DFT-calculation based in the singlet state is energetically more favorable. The electrochemical behavior of the synthesized compounds is also presented, including studies in acidic media. The electrochemical properties of the products vary in the presence of a double bond (cycloaddition of [(µ-S)2Fe2(CO)6] to alkynes), respect to a single bond (cycloaddition to alkenes).

Development and Validation of a Calibration Gauge for Length Measurement Systems.

Due to accuracy requirements, robots and machine-tools need to be periodically verified and calibrated through associated verification systems that sometimes use extensible guidance systems. This work presents the development of a reference artefact to evaluate the performance characteristics of different extensible precision guidance systems applicable to robot and machine tool verification. To this end, we present the design, modeling, manufacture and experimental validation of a reference artefact to evaluate the behavior of these extensible guidance systems. The system should be compatible with customized designed guides, as well as with commercial and existing telescopic guidance systems. Different design proposals are evaluated with finite element analysis, and two final prototypes are experimentally tested assuring that the design performs the expected function. An estimation of the uncertainty of the reference artefact is evaluated with a Monte Carlo simulation.

Study on Machine Tool Positioning Uncertainty Due to Volumetric Verification.

Volumetric verification is based on the machine tool (MT) kinematic model, along with its geometric errors. Although users often ignore the uncertainty of verification, the use of the MT as a traceable measurement system in the manufacturing process has increased the need for professionals to be aware of it. This paper presents an improvement in the MT kinematic model, introducing in it the influence of verification uncertainty sources. These sources have been classified into four groups: the MT, the measurement system itself, the measurement strategy, and the optimization strategy. As the developed model exhibits non-linear behavior, the Monte Carlo method was used to determine the influence of the measurement system on verification uncertainty using synthetic tests. In this manner, an improved estimation of the MT uncertainty can be obtained. Therefore, if the MT is used as a traceable measurement system, its accuracy should not be higher than the laser tracker (LT) verification influence. It hence shows the importance of LT influence.

Rpb4/7 facilitates RNA polymerase II CTD dephosphorylation.

The Rpb4 and Rpb7 subunits of eukaryotic RNA polymerase II (RNAPII) participate in a variety of processes from transcription, DNA repair, mRNA export and decay, to translation regulation and stress response. However, their mechanism(s) of action remains unclear. Here, we show that the Rpb4/7 heterodimer in Saccharomyces cerevisiae plays a key role in controlling phosphorylation of the carboxy terminal domain (CTD) of the Rpb1 subunit of RNAPII. Proper phosphorylation of the CTD is critical for the synthesis and processing of RNAPII transcripts. Deletion of RPB4, and mutations that disrupt the integrity of Rpb4/7 or its recruitment to the RNAPII complex, increased phosphorylation of Ser2, Ser5, Ser7 and Thr4 within the CTD. RPB4 interacted genetically with genes encoding CTD phosphatases (SSU72, FCP1), CTD kinases (KIN28, CTK1, SRB10) and a prolyl isomerase that targets the CTD (ESS1). We show that Rpb4 is important for Ssu72 and Fcp1 phosphatases association, recruitment and/or accessibility to the CTD, and that this correlates strongly with Ser5P and Ser2P levels, respectively. Our data also suggest that Fcp1 is the Thr4P phosphatase in yeast. Based on these and other results, we suggest a model in which Rpb4/7 helps recruit and potentially stimulate the activity of CTD-modifying enzymes, a role that is central to RNAPII function.

Volumetric verification of multiaxis machine tool using laser tracker.

This paper aims to present a method of volumetric verification in machine tools with linear and rotary axes using a laser tracker. Beyond a method for a particular machine, it presents a methodology that can be used in any machine type. Along this paper, the schema and kinematic model of a machine with three axes of movement, two linear and one rotational axes, including the measurement system and the nominal rotation matrix of the rotational axis are presented. Using this, the machine tool volumetric error is obtained and nonlinear optimization techniques are employed to improve the accuracy of the machine tool. The verification provides a mathematical, not physical, compensation, in less time than other methods of verification by means of the indirect measurement of geometric errors of the machine from the linear and rotary axes. This paper presents an extensive study about the appropriateness and drawbacks of the regression function employed depending on the types of movement of the axes of any machine. In the same way, strengths and weaknesses of measurement methods and optimization techniques depending on the space available to place the measurement system are presented. These studies provide the most appropriate strategies to verify each machine tool taking into consideration its configuration and its available work space.